The potential safety hazards associated with the Suzuki–Miyaura cross-coupling of aryl bromides with vinylboron species were evaluated. In the Suzuki–Miyaura cross-coupling of 1-bromo-3-(trifluoromethyl)benzene with potassium vinyltrifluoroborate in the presence of potassium carbonate (K₂CO₃) in 9:1 dimethyl sulfoxide (DMSO)/water at 80 °C, the thermal profile revealed a significant exotherm upon the addition of catalytic 1,1′-bis(diphenylphosphino)ferrocene palladium(II) dichloride [Pd(dppf)Cl₂]. Further investigations indicated that the exotherm was consistently higher and the reactions were faster in the studied aqueous systems compared to anhydrous conditions. Although under anhydrous conditions the exotherms were comparable among the studied cases, the rate of the exotherm was highly dependent on the choice of aryl electrophile, solvent, base, catalyst, as well as vinylboron species. In many of the studied cases the maximum temperature of a synthesis reaction (MTSR) was considerably higher than the boiling point of the solvent and/or the onset temperature of the DMSO decomposition, indicating that in the absence of active cooling the system could quickly exceed the boiling point of the solvent or trigger the decomposition of the reaction mixture to result in a runaway reaction.

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Suzuki-Miyaura芳族溴化物与乙烯基硼物种的交叉偶联相关的潜在安全隐患评估

评估了Suzuki-Miyaura与芳族溴化物与乙烯基硼物种交叉偶联的潜在安全隐患。在Suzuki–Miyaura在碳酸钾（K ₂ CO ₃）和9：1二甲基亚砜（DMSO）/水中在80°C的条件下，将1-溴-3-（三氟甲基）苯与乙烯基三氟硼酸钾交叉偶联，热曲线显示，添加催化的1,1'-双（二苯基膦基）二茂铁二氯化钯（II）[Pd（dppf）Cl ₂]。进一步的研究表明，与无水条件相比，在研究的水体系中放热始终较高，反应更快。尽管在无水条件下放热曲线在所研究的案例中是可比的，但放热速度在很大程度上取决于芳基亲电子试剂，溶剂，碱，催化剂以及乙烯基硼的选择。在许多研究案例中，合成反应（MTSR）的最高温度明显高于溶剂的沸点和/或DMSO分解的起始温度，这表明在没有主动冷却的情况下，系统可能会迅速超过溶剂的沸点或引发反应混合物的分解以导致失控反应。